Removal and recovery of heavy metal ions in fixed and semi-fluidized beds

Uptakes of heavy metal ions such as Pb²⁺ and Ni²⁺ were studied experimentally in fixed and semifluidized beds packed with a strong cation exchange resin, Amberlite 200. Single and binary aqueous solutions of lead and nickel ions were passed through ion exchange columns, and the exit concentrations were measured to get the breakthrough behavior of the ions. From the exit concentration profiles, the breakthrough time and the ion exchange capacity were evaluated. After removal of heavy metal ions from binary solution of lead and nickel ions until the breakthrough time, two metal ions were recovered by precipitation and resolubilization of lead. In this paper, the recovery yield and separation efficiency are rigorously discussed.     

The conditions of cationic exchange with the use of recycling polystyrene derivative,the product of sulfonation by silica sulfuric acid

Growing amount of waste plastics has become an environmental problem on a global scale. This study presents an investigation of the conditions of cleaning water from heavy metal ions using chemically recycled polystyrene. To get effective ion exchangers, the sulfonation of virgin polystyrene and expanded polystyrene wastes were obtained using silica sulfuric acid. As it turned out, the use of this solid sulfonating agent simplifies the separation of the polymeric product from the acid and the solvent in comparison to conventional sulfonation methods. The ion exchange behavior of copper and zinc cations in the yielded sulfonated derivatives of polystyrene was studied. Batch shaking adsorption experiments depending on contact time, pH, temperature, and dosage of adsorbate were carried out. The stability of resin to cyclical adsorption and regeneration (column experiment) was also investigated. We report that resins have a high adsorption efficiency with total ion exchange capacity (IEC) about 2.6 meq g^?1, which drops with decreasing pH owing to competition between protons H⁺ and metal cations, whereas with the increasing resin doses the removal of cations rises for a constant initial metal concentration. The speed of cation exchange for yielded adsorbents was even better than for commercial resins. After 360 cyclical adsorption and regeneration in column, resin had working IEC of about 2.3 meq g^?1. The study shows that cation exchange resin from polystyrene wastes can be used as an efficient adsorbent for the removal of heavy metal ions from water. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Oxidized cellulose: An application in the form of sorption filter materials

Oxidized cellulose (oxycellulose) was very effectively used in the form of filter sheets to remove some metal ions from water and from aqueous solutions. Furthermore, oxycellulose was applied in an ion‐exchange column and in a batch process. The mechanisms of the sorption process inside oxycellulose as well as the kinetics of sorption were studied. A comparison of oxycellulose and other adsorption components such as zeolites and ion‐exchange resins was made. The affinity of oxycellulose to metal ions was determined to be in the following order: Cd²⁺, Zn²⁺ > Ni²⁺ ? Ca²⁺ > Mg²⁺ ? Na⁺. The use of oxycellulose was very effective, especially in the form of sorption filters, because this allowed us to use a simple filtration process. Moreover, the specific loading amount of the filter cake was higher for filtration than for the column process under comparable conditions. Oxycellulose in a glass column behaved similarly to an ion‐exchange resin. It showed approximately constant efficiency until the sorption capacity of the adsorbent was exhausted, and then it suddenly dropped. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Removal of heavy metal-cyanide complexes by ion exchange

Simultaneous removal of heavy metal and cyanide ions in an ion exchange column is studied on the basis of formation of metal-cyanide complexes at high pH range. Strong base anion exchange resin beads were contacted with water containing heavy metal (Cu, Cd, Zn) and cyanide ions in semi-fluidized and fluidized beds. Compositions of the heavy metal-cyanide complexes formed for different heavy metal and cyanide concentrations are used to explain the ion exchange behavior. Ion exchange equilibrium data of this study were fitted well with the Langmuir isotherm. The ion exchange capacity of CNas metal complexes increased to about three times that of free cyanide due to higher selectivity of metal complexes on the anion exchange resin. The ion exchange efficiency of the three heavy metalcyanide systems decreases as the concentration ratio of cyanide and heavy metal increases. The regeneration rates of the regenerants used was in the order of NaSCN>NaCN>NaOH, and the regeneration rate of NaOH was substantially lower than other two. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Treatment of aqueous solutions containing nickel using crandallite‐type compounds

The removal of nickel from aqueous solutions streams has been investigated using an artificial amorphous crandallite‐type compound, CaAl₃(OH)₆(HPO₄)(PO₄) (Ca‐crandallite), synthesized in our laboratory. Equilibrium ion‐exchange isotherms in an aqueous medium of Ca²⁺/Ni²⁺ at different pH values at 293 K have been determined. The experimental equilibrium data were satisfactorily correlated using a Langmuir‐type empirical equation. At low pH values, the hydrogen ion competes with the heavy metal cation and the percentage removal of metal declines. It was found that the operating capacity of Ca‐crandallite with respect to the metal ion increased with the pH of the solution, in accordance with a second‐degree polynomial equation. However, the pH should not be allowed to rise to levels at which chemical precipitation as nickel hydroxide would occur, with 7.00 the highest value tested. Taking into account the variation of operating capacity with pH, the system exhibited a unique separation factor, namely all the experimental points can be described by a unique isotherm in a dimensionless form. The Ca‐crandallite showed a high capacity, 2.176 meq g^?1, for the exchange of Ni(II) from nickel nitrate solutions and the rate of exchange of metal increases with increasing solution temperature due to the enhancement of effective intraparticle diffusivity. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of a new guar gum 4‐hydroxybenzoic acid resin and its use for the separation of heavy metal ions in industrial effluents

Hydroxybenzoic acid group has been incorporated onto guar gum by modified Porath's method of functionalization of polysaccharides. The newly synthesized guar gum 4‐hydroxybenzoic acid (GHBA) resin was characterized by Fourier‐transform infrared spectroscopy, elemental analysis, ion‐exchange capacity, column reusability, and physicochemical properties. The distribution coefficient (K_d) values and effect of pH on chelation of these metal ions using batch method were studied. The separations of mixture of Fe²⁺, Zn²⁺, Cu²⁺, Cd²⁺, and Pb²⁺ metal ions on GHBA resin on the basis of their distribution coefficient at various pH were also achieved using column chromatography. The effect of experimental parameters such as pH, treatment time, agitation speed, temperature, adsorbent dose, initial metal ion concentration, and flow rate on the removal of metal ions has been also studied. GHBA resin is effective adsorbents for the removal of different toxic metal ions from aqueous solutions and follows the order: Fe²⁺ > Zn²⁺ > Cu²⁺ > Cd²⁺ > Pb²⁺. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Highly porous,water-swellable,and reusable chelating polymeric gels for heavy metal ion removal from aqueous waste

Sequestration and removal of heavy metal ions from aqueous solutions pose multiple challenges. Ease of synthesis, high adsorption capacity and ease of regeneration are important considerations in the design of polymeric adsorbent materials developed for this purpose. To meet this objective, a new approach was used to design and synthesize a highly porous polystyrene-based resin (IDASR15) bearing iminodiacetate functional groups in every repeat unit by free radical polymerization with N, N'-methylenebisacrylamide as crosslinker followed by base hydrolysis. The physiochemical chemical properties of the resin were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, equilibrium swelling value (ESV) and thermogravimetric analysis. Metal uptake capacity of IDASR15 towards low concentrations of various toxic heavy metal ions such as Cu²⁺, Cd²⁺, Mn²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Co²⁺, Co³⁺, Cr³⁺, Fe²⁺, Fe³⁺, and Al³⁺ were investigated from their aqueous solution by batch method and found to be 0.943–2.802 mmol/g. The maximum capacity was 2.802 mmol/g obtained for Cu²⁺ ion at pH 5. The potential for regeneration and reuse has been demonstrated with Cu²⁺ ion by batch and column methods. The reported results suggest that IDASR15 is a highly efficient and porous complexing agent for commonly found toxic metal ions in aqueous streams with a high ESV of 68.55 g of water/1.0 g of IDASR15. It could also be reused ~99.5% of adsorption efficiency which is very promising and holds significant potential for waste-water treatment applications.     

Equilibrium data of the exchange of Cu2+, Cd2+ and Zn2+ ions for H+ on the cationic exchanger Lewatit TP‐207

Equilibrium ion exchange isotherms in aqueous medium of H⁺/Cu²⁺, H⁺/Zn²⁺ and H⁺/Cd²⁺ on a weak acid resin Lewatit TP‐207, at different pH values and at 298 K have been determined in order to assess the possibility of using ion exchange to eliminate heavy metal ions from industrial aqueous liquid streams. The experimental equilibrium data have been satisfactorily correlated using a Langmuir‐type empirical equation. It was found that the operating resin capacity with respect to each metal ion increased with increase in solution pH, in accordance with a second‐degree polynomial equation. Taking into account the variation of operating capacity with pH, each system exhibited a unique separation factor, namely all the experimental points can be described by a unique isotherm in a dimensionless form. Resin Lewatit TP‐207 exhibited the following selectivity order: Cu²⁺ > Zn²⁺ > Cd²⁺ at 298 K. Copyright © 2004 Society of Chemical Industry     

Packed-bed columns with dye-affinity microbeads for removal of heavy metal ions from aquatic systems

A dye ligand Cibacron Blue F3GA, was covalently coupled with polyhydroxyethylmethacrylate (PHEMA) microbeads in the 150–200 μm particle size range. The sorbent carrying 22.3 μmol Cibacron Blue F3GA per gram of polymer was then used to remove Pb(II), Cd(II), Cu(II) and Zn(II) from aqueous solutions in a packed-bed column system. Heavy metal ion adsorption capacity of the column was investigated as a function of heavy metal ion-bearing solution flow rate and the inlet heavy metal ion concentration. The maximum metal ion uptake values found were: 80.60, 96.98, 78.36, 103.98 μmol/g polymer for Pb(II), Cd(II), Cu(II) and Zn(II), respectively. The heavy metal adsorption capacity of the microbeads decreased with an increase in the circulation rate of aqueous solution. The order of affinity based on molar uptake was Zn(II)>Cd(II)>Pb(II)>Cu(II). Removal percentages of heavy metals related to flow time were determined for different flow rates and initial metal ion concentrations. It was observed that PHEMA microbeads carrying Cibacron Blue F3GA can be regenerated by washing with a solution of nitric acid (0.05 M). The desorption ratio was as high as 98.5%.     

Synthesis,Characterization, and Applications of a New Ion Exchanger Tamarind 4-aminobenzoic Acid (TABA) Resin in Industrial Wastewater Treatment

Chromatographic column separations of toxic metal ions from industrial wastewater were achieved in acid media at optimized (K_d) values with a synthesized cation exchange TABA resin. The prepared TABA resin was characterized by FTIR, elemental, and thermogravimetric analysis. Studies of total ion exchange capacity, resin durability, and swelling were carried out. The distribution coefficient values of metal ions, viz Cu²⁺, Fe²⁺, Zn²⁺, Cd²⁺ and Pb²⁺ at different pH, were also studied using a batch equilibration method. The different factors affecting metal ions adsorption on this substrate, such as treatment time, agitation speed, and temperature, were studied in detail.     

MECHANISM OF POLYMER-BASED SEPARATIONS. III. METAL ION LOADING CAPACITIES OF REACTIVE POLYMERS WITH SPECIFIC RECOGNITION MECHANISMS

The metal ion selectivity series displayed by a reactive polymer, the phosphinic acid ion exchange/redox resin, was determined from equinormal solutions of 1 milliequivalent metal ion per milliequivalent of polymer ligand sites and compared to results from trace ion solutions. It was found that intervention by the recognition mechanism (i.e., reduction) with Hg(II) and Ag(I) ions from pH 2 aqueous solutions led to high resin loading capacities. Thus, the phosphinic resin/Hg(II) interaction displayed a log D of 3.88, compared to 3.80 from a 10^-4 N solution, indicating that the recognition mechanism obviated any influence of a loading effect. The loading effect was apparent in Fe(III) complexatign wherein a log D of 4.94 was found from a 10^-4 N solution and 0.40 from the equinormal solution. The solution acidity was also an important determinant of selectivity: the series was Fe > Hg > Mn > Ag from 4N HNO₃ and Hg > Ag > Mn > Fe from 0.01N HN0₃. The performance of the phosphinic acid resin was contrasted to that from the non-reactive (i.e., solely ion exchanging) phosphonic acid resin.     

Ion exchange with irreversible reaction in deep fluidized beds

The exchange of CI^? ion between dilute aqueous solutions of hydrochloric acid and the ion exchange resin IRA-425 in fluidized beds was studied in a laboratory size column. Analysis of the experimental data showed that axial mixing of particles in deep beds was incomplete and also that packed and fluidized bed break-through curves were similar. A model is proposed describing the bed as a series of mixing stages for solids with axially dispersed flow of liquid. Data are presented in support of such a concept. An empirical method is proposed for prediction of the break-through curves at various operating conditions, requiring only a very limited amount of experimentation.     

Lead removal from aqueous solutions by 732 cation‐exchange resin

Kinetics and thermodynamics of the removal of Pb²⁺ from an aqueous solution by 732 cation‐exchange resin in hydrogen type (732‐CR) were studied in the temperature range of 298–328 K and Pb²⁺ concentration range of 5–50 mol/m³. The effects of ion exchange temperature and initial lead ion concentration on the time evolution of the experimental concentration for the metal ion were investigated. Ion exchange kinetics of Pb²⁺ onto 732‐CR follow the Nernst‐Planck equation and unreacted‐core model (UCM). The diffusion coefficients of counter ions and the efficient diffusion coefficient of lead ions within the resin were calculated. The results show that the ion exchange process is favoured under the particle diffusion control mechanism. The ion exchange isotherm data agreed closely with the Langmuir isotherm. The maximum monolayer exchange capacity for Pb²⁺ was found to be 484.0 mg/g at 308 K. Thermodynamic studies show that Pb²⁺ onto 732‐CR is spontaneous and exothermic in nature. The ion exchange processes were verified by Energy Disperse Spectroscopy (EDS).     

Thiourea modified hyper‐crosslinked polystyrene resin for heavy metal ions removal from aqueous solutions

A hyper‐crosslinked resin chemically modified with thiourea (TM‐HPS) was synthesized, characterized, and evaluated for the removal of heavy metal ions (Pb²⁺, Cd²⁺, and Cu²⁺) from aqueous solutions. The structural characterization results showed that a few thiourea groups were grafted on the surface of the resin with a big BET surface area and a large number of narrow micropores. Various experimental conditions such as pH, contact time, temperature, and initial metal concentration of the three heavy metal ions onto TM‐HPS were investigated systematically. The results indicated that the prepared resin was effective for the removal of the heavy metal ions from aqueous solutions. The isotherm data could be better fitted by Langmuir model, yielding maximum adsorption capacities of 689.65, 432.90, and 290.69 mg/g for Pd²⁺, Cd²⁺, and Cu²⁺, respectively. And the adsorption kinetics of the three metal ions followed the pseudo‐second‐order equation. FTIR and XPS analysis of TM‐HPS before and after adsorption further revealed that the adsorption mechanism could be a synergistic effect between functional groups and metal ions and electrostatic attraction, which may provide a new insight into the design of highly effective adsorbents and their potential technological applications for the removal of heavy metal ions from aqueous solutions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45568.     

Selective adsorption of Au3+ from aqueous solutions using persimmon powder‐formaldehyde resin

A new adsorption resin has been developed by immobilizing persimmon powder with formaldehyde, and its adsorption properties to Au³⁺ were investigated in detail. The resin exhibited outstanding selective adsorption capacity towards Au³⁺ from acidic aqueous solutions (pH 2.0), which the equilibrium adsorption capacity was high up to 3025.20 mg g^?1 at 323 K. The resin exhibited 100% adsorption of Au³⁺ within 8 h, and the experimental data were well fitted with the pseudo‐first/second‐order rate model. The adsorption isotherms could be well described by Freundlich equation. The column studies suggested that the resin was effective for the adsorption of Au³⁺ from aqueous solutions, and the loaded Au³⁺ could be easily desorbed by acidic thiourea solution. The adsorption of Au³⁺ was an endothermic reductive adsorption process. This suggested that the resin can be used as an active biosorbent for the recovery of Au³⁺ from aqueous environment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3937–3946, 2013     

SYNTHESIS AND CHARACTERIZATION OF THE ION EXCHANGE PROPERTIES OF A SPHERICALLY GRANULATED SODIUM ALUMINOPHOSPHATESILICATE

ABSTRACT

Spherically granulated sodium aluminosilicophosphate (APS) of the empirical formula Na₄Al₄PS₁₈O_46.5 18H₂O was synthesized by a gel method. The APS was characterized by elemental analysis, X-ray diffraction, TGA and ²⁷AI, ²⁸Si and ³¹P MAS NMR spectroscopy methods. Ion exchange of alkali, alkaline earth and some other divalent metal cations by APS was studied in batch conditions. It was found that the APS has a cation exchange capacity of 2.5 meq/g and exhibits rapid kinetics of ion exchange. The ion exchange isotherms of alkali, alkaline earth and some other divalent cations were determined and the corrected selectivity coefficients as a function of metal loading were analyzed. It was found that APS exhibits a high affinity for cesium ion, a moderate affinity for some heavy metal cations (Pb²⁺, Zn⁺) and a low affinity for alkali and alkaline earth metal ions. A testing of the APS in complex solutions suggests that it could be a promising exchanger for treatment of some specific nuclear waste and contaminated environmental and biological liquors from radioactive cesium and toxic heavy metal ions.     

Copper-selective chelating resins. II. Column extractions

Two chelating resins based on poly(glycidylmethacrylate-co-ethyleneglycol dimethacrylate) and two based on poly(styrene-co-divinylbenzene) have been used in small-scale column extractions of Cu(II) from sulphate solutions containing 1.0 mg l⁻¹ of metal ion at pH 5. Two of the resins bearing 2-aminomethylpyridine residues with saturation capacities up to ∼ 15 g Cu(II) l⁻¹ resin showed sharp breakthrough profiles and rapid exchange kinetics. The other two with higher ligand loading displayed shallow profiles and did not reach saturation capacity, indicating a significant proportion of the ligand groups to be inaccessible under the conditions employed. For a column of 10 ml bed volume, increasing the flow rate of the feed solution from 1 ml min⁻¹ progressively to 30 ml min⁻¹, using one of the more efficient resins, showed that above a rate of ∼ 5 ml min⁻¹ the bulk movement of ions through the column was too fast for all the resin-bound ligands to be accessed. As a result breakthrough moved to lower volumes and the working capacity dropped. No difference was found in the elution of all four resins with 1 M H₂SO₄ at a flow rate of 1 ml min⁻¹. In all cases Cu(II) was rapidly and efficiently eluted from the column.The selectivity properties of the two efficient resins in extracting Cu(II) ions from a solution containing a large excess of Zn(II) ions were also investigated. The effect of a 250-fold excess of Zn(II) proved negligible in both cases, and Cu(II) was rapidly and selectively extracted with a separation factor of ∼ 900: 1 in the case of the polystyrene-based resin, and ∼ 500: 1 in the case of the methacrylate-based species.In terms of kinetic performance and metal ion selectivity (in both loading and elution) the results of the batch extraction experiments were confirmed in these column tests, hence proving the predictive value of careful batch testing. On considering kinetic factors, capacity factors and metal ion selectivity factors, a resin carrying a 2-aminomethylpyridine group attached to a polymethacrylate backbone proved to be the optimum one.     

Development of an ion exchange system for plating wastewater treatment

Ion exchange technology was applied to this study to treat nickel ion from plating wastewater which contains heavy metal, bringing environmental problems such as chromium, zinc, copper, and lead. To separate nickel ion from wastewater, the nickel recovery unit (NRU) used a column packed with strongly acidic cation resin. The leak of the ion appeared when rinse water that has a concentration of 1.8 g-Ni/L-distilled water flowed into the NRU as much as 20 times the bed volume. At this time, the capacity of resin packed in the column was 1.7 meq/ml and over 99% nickel ion was removed. Sulfuric acid was employed with a reagent in order to regenerate nickel ion from the resin adsorbed. Nickel ion recovered by sulfuric acid was obtainable up to 120 g-Ni/L. The concentration of sulfuric acid was 2N and space velocity was 2/h. Acid retardation unit (ARU) experiment could be accomplished by deacidification to control the pH of the solution to recycle in the plating process. The composition was 30 g-Ni/L and the pH maintained was over 3.0.     

Removal of Cu2+ and Pb2+ ions from aqueous solutions by starch-graft-acrylic acid/montmorillonite superabsorbent nanocomposite hydrogels

In this study, the removal of copper(II) and lead(II) ions from aqueous solutions by Starch-graft-acrylic acid/montmorillonite (S-g-AA/MMT) nanocomposite hydrogels was investigated. For this purpose, various factors affecting the removal of heavy metal ions, such as treatment time with the solution, initial pH of the solution, initial metal ion concentration, and MMT content were investigated. The metal ion removal capacities of copolymers increased with increasing pH, and pH 4 was found to be the optimal pH value for maximum metal removal capacity. Adsorption data of the nanocomposite hydrogels were modeled by the pseudo-second-order kinetic equation in order to investigate heavy metal ions adsorption mechanism. The observed affinity order in competitive removal of heavy metals was found Cu²⁺ > Pb²⁺. The Freundlich equations were used to fit the equilibrium isotherms. The Freundlich adsorption law was applicable to be adsorption of metal ions onto nanocomposite hydrogel.     

A MECHANISM FOR ENHANCING IONIC ACCESSIBILITY INTO SELECTIVE ION EXCHANGE RESINS

ABSTRACT

A bifunctional monophosphonic/sulfonic acid ion exchange resin with high capacity has been synthesized. Metal ion studies have been carried out with europium, americium, and ferric nitrate in solutions of varying acidity, with and without sodium nitrate added. The bifunctional resin complexes far higher levels of Eu(III) from 0.5 and 1 N nitric acid than the monofunctional phosphonic acid resin. It is postulated that the sulfonic acid ligand provides an access mechanism for the metal ions into the polymer matrix by hydrating the matrix and preventing its collapse in high ionic strength solutions thus allowing for rapid ionic complexation by the selective phosphonic acid ligands. The bifunctional monophosphonic/sulfonic acid resin has both ligands bound to a polystyrene support. It complexes higher levels of metal ions than a comparable resin differing only by having the monophosphonic acid ligand directly bound to the C-C backbone. Results are compared to a diphosphonic / sulfonic acid resin.